Flooring composition of blown petroleum residue and asbestos fiber



Patented June 3, 1952 FLOQRINGeCQMEOSITIQNTQE"BLQWN PETROIJEUM- RESIDUEA'ND ASBES- TOS' FIBEBi Harry W. .Lawson; hicago, Ills .assignorzto Alp ne.-

Corporation, Chicago, 111.,

v Illinois.

a I corporation of No =-Drawing. Application J anuary---26,-- 1948;

- Serial No. 4,465

v2. Claims.

This;m.VentiQn relates 1. to: resins; obtained. by nrqcessing certain by-products of ,;the. petroleum industry,-, to; a methodv of forming said resins, and c-tonovel'floor tile and similar compositions, wherein. certain of said resins exhibit unique advanta es: as binding agents.-

Hithertoheavy-petroleum residues, for-example, stillbottoms and oils from which distillableahyd-rocarbons have 1 been removed-have been. ain-blown ,;usually-in the-presence of a catalyst attemperaturesof 400F. to 550 F. The melting points of the resins thus obtained regulax-1y. lie within therangeof 220 E. up to 250F. suchlresinsttakenalone lare too brittle to serve asgbi-nders ingthej. manufactur of floor tile and similan flooring compositions; so it has been a reeular.-' practice to. combine these; resins with varioussplasticizersz. inntlce .-f.orm-oi fat y cid pitches; obtained from vegetable and animal sources; "While: such plasticizers:reduce ;-the brittleness 0f.;.the.- above -resins, they possess-the important disadvantages. ofbeing-saponified by; alkaline detergents; The: result is ;;that floor tiles; con.- taining such,plasticized resins, when subjected addition, thereto, of. any plast c r-0tv etab1a to 1 the; ordinary 7 amount of: scrubbing with alkalinegsoapsand similar. detergents; tend to become weakened; and irasmcnted,-. particularly along their edges; so that the life of such tiles is un: duly. limited;

.Lhave discovered' that in making floorttile and similar. floori z omp sitions. the incorporat on of plasticizing agents with resins ;ob tain;ed;from mineral oil sources can be alloidedeewith the consequent elimination of the disadv nta es in; hermeinsu h-agent as componen sof; bind rs for flooringcompositions In: the practice lofmy discovery I employ certain novel method steps whereby to form novel resins including: resins that are particularly well adapted for use as binders in-the manufacture of flooring compositions;- all of said resins possessing marked resistance to saponification by alkaline agents.

:-A principalobjectof my invention is-to provide a method of forming, from raw materials of petroleum origin-,1- unsaponifiable resins-that possess at ordinary temperaturesthe, optimal degrees of coldi-floyv and of flexibility thathave been sought for binders for flooring composition.

Another principalobjeet of my invention is to proyide an unsaponifiable resin, substantially-entirelyderived' from petroleum, that possesses-by itself "the aforementioned optimal characteristics as to cold flow-and flexibility.

Another objectisto provide angunsaponifiable resin of mineral origin that is adaptedg without r; animal ori i to: s rve; s; a b nder-.-

the manufacture; of so. :ca11 d; snha1t tile- Still another object is totprovidea-novelfloor' tile; or :fiOQIii lEs JP Sifi I I w e inthe-bin component consists: entirelyiqof a; resin; derived: from; the source; and? possessing... theenh sical characteristics. set. forth. in the secondiparagraph' next, above;

- otherobi ts. nd es,.-fQr,:.my inv ntion. WilLapD arasthe.descripti n;thereoftp foce ds- An illustrative; examplewof, thepractice of my novelaprocess is thefollowing:

As a: raw material; I prei r blyremploy; a bar: tially. polymerized residue; from: era kedjsasoline that has been prepared.by;the.asQ-,cal1edt ear ower" process This raw aterial; poss sses substantiallyathe following chara teristics Its-@9111: to.

point lies :Within atherlfangeimmabQHF- O, E about-;80.?: FE and. itss-iodine number; lies. ithin; the range;from-.aboutl to about 2&9. .-'I:.:also; may use as a rawmaterialjanyrsim lanpetmleumr residue havingzthe,;:characteristics Just. stated;

.With a quantitywof said raw-material lainoorr pora-te acatalyst,- generally inv the;proportionrof: one ounceofcatalyst to about 10 poundsofirfiw materiaL. The amountyof catalyst, .howevenpmay be #varied from about. one-half; ounce to 1 about. 2 .ouncesper l0 pounds.of-raw-material. The quantity. of catalyst-,thusl-ranges from. about .3.. per; cent to about 12.2"; percent; calculated: on the raw material.

Thecatal'yst preferably is. a. naphthenate oi: manganese; iron or; lead, one, suitablexmixture of. such metallicna-phthenates, preferably icon taining: aboutfi *per cent of "metallic component.

Nevertheless, "any other. substance that sis; compatiblejwith the raw material, that is suitably (iispersible therein, and that isadapted for'catalyzing the resinification'thereof', without reducingthe iodine-.numberof: the product below: about 160, also may be-employed as acatalyst:

- I :next. heat the ;,mixture of 'raw material and catalyst" in a: retortor. other suitablevessels: preferably at atmospheric pressure; at the-same time bubbling air through the a mixture. I"ha'.ve=:found ploy-depends "largely upon whether or not-J1 carrymy operating temperature up toathermaximum of 3:75" F. Atrthe :latter temperature.my:heating period ordinarily lies within the range of about-- 3 one hour to about 15 hours, depending upon the melting point of the particular product that I desire; which melting point may lie within the range from about 70 F. to about 190 F. In general, the melting point of the product rises about 5 F. for each hour during which the raw material is processed at a temperature of 375 F.

At times it is a matter of practical advantage to employ lower heating temperatures; although. for example, when the heating temperature lies within the range from about 270 F. to about 300 F., the time required to form a product having a given melting point is substantially longer than is the case at 375 F.

In the bubbling of air through the heated mixture of raw material and catalyst I preferably employ as great a volume of air, with as small bubbles and as much turbulence, as possible, having in view (a) the increasing resistance to the passage of air through the heated mixture as resinification proceeds, and (b) the avoidance of excessive spattering of the contents of the retort or treating vessel.

The products derived from the foregoing raw material, by the treatment described above, are resins that have melting points within the range from about 70 F. to about 190 F., and iodine numbers within the range from about 160 to about 220. All of these resins are characterized by marked resistance to saponification by alkaline agents. Of these resins those that have melting points below about 150 F. are adapted for a variety of uses that will be appreciated by those skilled in the art, where a desideratum of such a resin is unsaponifiability.

Of the novel resins that are products of the method described hereinabove, those having melting points within the range of temperatures from about 150 F. to about 190 F. are especially adapted for use as sole binding materials in the manufacture of so-called asphalt flooring tile, because they not only are resistant to saponification, as aforesaid, but they also possess by themselves the desirable cold flow and flexibility characteristics that are principal objects of my invention. In the manufacture of asphalt flooring tile my novel resins, having melting points within the range last above stated, can be used as binders without admixture with any other binding material or with any plasticizing agent. These same resins meet the specifications for such binders, as set forth in the Government publication entitled Federal Specifications for Tile-Asphalt. SS-T-30d-1A. From Federal Standards Stock Catalog, Section 4, Part 5.

a I have found-that I can form a lighter-colored product from the foregoing raw material, without adversely affecting the desirable properties just stated, by humidifying, an any suitable manner, the air that is blown through the heated mixture of the raw material and catalyst.

An example of a novel composition suitable for floor tile is an intimate mixture of the following ingredients, in percentages by-weights: A resin resulting from the practice of my novel method, melting preferably at about 180 F., about 28 per cent to about 30 per cent; pigment, from about 2 per cent to about per cent; the balance to make 100 per cent, a suitable wear-resistant residue having initially a pour point within the range from about 30 F. to about and an iodine number within the range from about 180 to about 240; said treatment comprising essentially the step of air blowing said residue in the presence of a catalyst at a temperature in the range from about 270 F. to 375 F.; said binder having a melting point within the range from about 70 F. to about 190 F. and an iodine number not substantially lower than nor substantially higher than 220; said binder imparting to said flooring composition high resistance to saponification by alkaline agents and an efiective degree of cold flow and of flexibility; said composition comprising, in intimate admixture, in parts by weight, from about 28 parts to about 30 parts of said resinous binder, about 2 parts to about 10 parts of pigment, and the balance, to make a total of 100 parts, of short asbestos fibers.

2. A flooring composition which is free from a plasticizing agent as an ingredient thereof; a component of said composition being a resinous binder formed by treatment of a petroleum residue having initially a pour point within the range from about 30 F. to about 80 F., and an iodine number within the range from about 180 to about 240; said treatment comprising essentially the step of air blowing said residue in the presence of a catalyst at a' temperature in the range from about 270 F. to 375 F.; said binder having a melting point within the range from about 70 F. to about F. and an iodine number not substantially lower than 160 nor substantially higher than 220; said binder imparting to said flooring composition high resistance to saponification by alkaline agents and an effective degree of cold flow and of flexibility; said composition comprising, in intimate admixture, in parts by weight. from about 28 parts to about 30 parts of said resinous binder; from about 2 parts to about 10 parts of pigment; not less than 70 per cent of the balance, needed to make a total of 100 parts, of short asbestos fibers; and the remainder of said balance in the form of a powdered filler from the class consisting of limestone, clays, sands and slags.

HARRY \V LAWSON.

REFERENEES CITED UNITED STATES, PATENTS Number 8 Name Date 5 1,888,044 Morrell Nov. 15, 1932 2,008,103 Hyman July 16, 1935 2,085,455 Bjerregaard Mar. 31, 1936 2,390,189 Soday De'c.-4, 1945 2,559,985 Morris July 10,1951

OTHER REFERENCES Lee et al., Paint, Oil 8; Chem. Rev., pages 16-20 (January 8, 1948). 

1. A FLOORING COMPOSITION WHICH IS FREE FROM A PLASTICIZING AGENT AS AN INGREDIENT THEREOF; A COMPONENT OF SAID COMPOSITION BEING A RESINOUS BINDER FORMED BY TREATMENT OF A PETROLEUM RESIDUE HAVING INITIALLY A POUR POINT WITHIN THE RANGE FROM ABOUT 30* F. TO ABOUT 80*F., AND AN IODINE NUMBER WITHIN THE RANGE FROM ABOUT 180 TO ABOUT 240; SAID TREATMENT COMPRISING ESSENTIALLY THE STEP OF AIR BLOWING SAID RESIDUE IN THE PRESENCE OF A CATALYST AT A TEMPERATURE IN THE RANGE FROM ABOUT 270*F. TO 375*F.; SAID BINDER HAVING A MELTING POINT WITHIN THE RANGE FROM ABOUT 70* F. TO ABOUT 190* F. AND AN IODINE NUMBER NOT SUBSTANTIALLY LOWER THAN 160 NOR SUBSTANTIALLY HIGHER THAN 220; SAID BINDER IMPARTING TO SAID FLOORING COMPOSITION HIGH RESISTANCE TO SAPONIFICATION BY ALKALINE AGENTS AND AN EFFECTIVE DEGREE OF COLD FLOW AND OF FLEXIBILITY; SAID COMPOSITION COMPRISING, IN INTIMATE ADMIXTURE, IN PARTS BY WEIGHT, FROM ABOUT 28 PRTS TO ABOUT 30 PARTS OF SAID RESINOUS BINDER, ABOUT 2 PARTS TO ABOUT 10 PARTS OF PIGMENT, AND THE BALANCE, TO MAKE A TOTAL OF 100 PARTS, OF SHORT ASBESTOS FIBERS. 